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Abstract
Doppler-limited, steady-state, linear absorption spectra of 127 I2 (diatomic iodine) near 675 nm were recorded with an internally-referenced wavelength modulation spectrometer, built around a free-running diode laser using phase-sensitive detection, and capable of exceeding the signal-to-noise limit imposed by the 12-bit data acquisition system. Observed I2 lines were accounted for by published spectroscopic constants.
Pressure broadening and pressure shift coefficients were determined respectively from the line-widths and line-center shifts as a function of buffer gas pressure, which were determined from nonlinear regression analysis of observed line shapes against a Gaussian-Lorentzian convolution line shape model. This model included a linear superposition of the I2 hyperfine structure based on changes in the nuclear electric quadrupole coupling constant. Room temperature (292 K) values of these coefficients were determined for six unblended I 2 lines in the region 14,817.95 to 14,819.45 cm−1 for each of the following buffer gases: the atoms He, Ne, Ar, Kr, and Xe; and the molecules H2, D2, N2, CO2, N2O, air, and H2O. These coefficients were also determined at one additional temperature (388 K) for He and CO2, and at two additional temperatures (348 and 388 K) for Ar. Elastic collision cross-sections were determined for all pressure broadening coefficients in this region. Room temperature values of these coefficients were also determined for several low-J I2 lines in the region 14,946.17 to 14,850.29 cm−1 for Ar.
A line shape model, obtained from a first-order perturbation solution of the time-dependent Schrödinger equation for randomly occurring interactions between a two-level system and a buffer gas treated as step-function potentials, reveals a relationship between the ratio of pressure broadening to pressure shift coefficients and a change in the wave function phase-factor, interpreted as reflecting the “cause and effect” of state-changing events in the microscopic domain. Collision cross-sections determined from this model are interpreted as reflecting the inelastic nature of collision-induced state-changing events.
A steady-state kinetic model for the two-level system compatible with the Beer-Lambert law reveals thermodynamic constraints on the ensemble-average state-changing rates and collision cross-sections, and leads to the proposal of a relationship between observed asymmetric line shapes and irreversibility in the microscopic domain.
